CA1305144C - 6,7-dihydro-[1,2,4]-triazolo[1,5-a][1,3,5]triazine-2- sulphonamides, processes for their preparation and their use as herbicides and plant growth regulators - Google Patents

Abstract

ABSTRACT
The invention relates to new 6,7-dihydro-[1,2,4]triazolo-[1,5-a][1,3.5]triazine-2-sulphonamides of general formula I

Description

~3~

The invention rela~e~ to new 6,7-dihydro-[1,2,9]-triazolo[l,5-a][l,i,5]triazine-2-sulphonamides. proces~es for their p~eparation and their use as herbicides and plan~ growth regulators.

It is known tha~ triazolopyrimidinesulphonamides ~9_ ~9-possess herbicidal activi~y (~P 142)152 andA150~974).
However the herbicidal activity of the known compounds is ~ not sufficien~ and/or selectivity problems can occur in ; important crops, The object of ~he present invention is ~o make new compounds that do not show the disadvantages of the known compounds and have improved biological properties.
It has now been found that 6,7-dihydro-[1,2,4~triazolo-t1,5-a~[l,3,5]triazine-2-sulphonamides of yeneral formula I

Ar~

in which : Ar is a phenyl, naphthyl, pyridyl or ~hienyl group of general formula ,: :

~ 25 `~;

R,,~R2 ~ R~ $R~, R~,~

10 ' R~R ~

Rl, R2, R3, R4 and R5 are ths same or dlfferent and are hydrogen. a Cl-C6-alkyl, C2-C6-alkenyl or Cz-C6-alkynyl group, each of which is optionally substi~uted by one or ~ore of the same or different halo, hydroxy, halo-Cl-C4-alkyl, Cl-C4-alkoxy, halo-Cl-C4-alkoxy, Cl-C4-al~yl~hio, Cl-C4~-alkylsulphinyl or Cl-C4-alkylsulphonyl, halogen, Cl-Cg-alkoxy, a group Rg-O-CO, a carbamoyl ~3~

R10~ 10~
group N-C0-, an amino group N-, cyano, Rll E~ll : nitro, a sulphur containing group Rg-S(O)n-, an acyl group Rg-CO, a group Rg-O-CO-(CH2)n, or phenyl or phenoxy, both of which are op~ionally substi~uted by one or more of Cl-Cg-alkyl, halo or nitro, R6 is hydrogen, an acyl group Rg-CO, a group Rg-O-CO-, Cl-C~-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, phenyl-Cl-C~-alkyl, a carbamoyl 10 ~
~ group N-C0-, an alkali metal atom, a single : Rll ~
~; 15 metal equivalent of an alkaline eart~ or other metals :or ammonium group, optionally substituted by -C6-al~Yl, ~
R7 and R8 are the same or different and are hydrogen, a Cl-C6-alkyl, C2-C6-alkenyl or Cz-C6-alkynyl group, each of which is optionally substituted by halo and/or Cl-C9-al~oxy, a phenyl-Cl-C6-alkyl, phenyl-C2-C6-alkanyl or phenyl-Cz-C6-alkynyl group, each of which is optionally substitut:ed by halo, Cl-C4-alXyl, Cl-C4-alkoxy, Cl-C4-alkoxy-Cl-C~-alkyl or ~: - 3 -~3~53L~

halo-Cl-C4-alkyl, phenyl, substituted by Rl, R2, R3, Rg and R5, an acyl group Rg C0, a group Rg-O-CO, a group Rg-0-CO~tCH2)n~ a Rlo ~
carbamoyl group N-C0-, or a sulphonyl group R
R -S0 , is hydrogen, a Cl-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or phenyl-Cl-C4-alkyl group, each of which is optionally substi~uted by one or more of the same or different halo, hydroxy or Cl-C4-alkoxy, or phenyl, optionally substituted by halo, nitro or Cl-C4-alkyl, ~ Rlo and Rll are the same or different and are : ; 15 hydrogen, a Cl-C6-alkyl, C2-C6-alkenyl or Cz-C6-alkynyl groupO each of which is optionally substitu~ed by one or more of the same or different halo, hydroxy or Cl-C4-alkoxy, or Rlo and Rl1 together with the adjacent nitrogen form a pyrrolidinyl, piperidino or morpholino ring, ~; ~ is oxygen or sulphur, and n is 0, 1 or 2, show an interesting herbicidal and plant growth regula~t :~ activity.
~ 25 The term "halogen" in relationship with alkyl, ~3~5~

alkenyl, alkynyl or phenyl means that one or more hydrogen atoms are replaced by one or more halogen atoms.
The term "halogen" mean~ fluorineO chlorine, bromine and iodine.
6,7-Dihydro-[1,2,4]~riazolorl,5-a~tl,3,5]tr}azine-2-sulphonamides of general formula I which show par~icularly good activity are those in which Ar is a phenyl group of general formula R,, RS
1~ ~<

~: R2 R1 Rl and R5 are the same or d1Pferent and are ; lS halogen, me~hyl, trifluoromethyl, nitro~ methoxy or methoxycarbonyl, R2, R~ and R4 are the same or different and are hydrogen, halogen, trifluoromethyl or a Cl-C4-alkyl group, R6 is hydrogen, a single eguivalent oP a metal : or a Cl-C4-acyl group, and R7 and R8 are the same or different and are Y g ~: l 4 Y ~ l 6 kyl, C2-C~-alkenyl or phenyl.

:;
~: _ 5 _ ~3~: L4~L

The compounds of the invention of general Por~ula I
can be prepared for example by A) reacting an amine of general formula II, A~-NH-R6 ~II) in which Ar has the meaning give~ above and R6 is hydrogen, C1-C6-acyl, C2-C~-al~enyl or C2-C6-alkynyl, with a sulphonyl cbloride of general formula III

R ~111) in which R7, R~ and X have the meaDings given above in a suitable solvent and in the presence of an acid acceptor, or :
B~ reacting a compound of general formula IV
: 20 : /H

IV) A2~ N NH2 R 1) in which Ar has t~e meaning given above and R6 is hydrogen, cl-C5-acyl, C2-C6-alkenyl or C2-C6-alkynyl, with a~ isocyanate or isothiocyana~e of formula V

R7-NCX ~V) in which R7 and X have the meaning~ given above in a suitable solvent, optionally in the pre~ence of an acid acceptor andJor cataly~t, and reacting the re~ulting compound of general formula 'VI
X

Ar-N--S~I~N~ NH2 IVI) ~:
in which Ar, R7 and X ha~e the meanings given above and R6 is hydrogen, Cl-C6-acyl, ~ C2-C6-alkenyl or C2-C6-alkynyl, with an ; ortho ester of general formula VII
- : 20 ~ R~-C(ORg)3 (VII) in which Rg has ~he meaning given above, excep~
hydrogen, and R8 i6 ~ydrogen, a 1 6 Y ~ 2 6 Y
C2-C~-alkynyl group, each of which i8 : op~ionally ~ubstituted by ha}o andJor ~: _ 7 .

:~L3 Cl-C4-aIkoxy a phenyl-Cl-C6-alky phenyl-C2-C6-alkenyl or phenyl-C2-C6-alkynyl group, ea~h of which is optionally sub~tituted by ha:lo, Cl-Cg-alkyl, Cl-C~-alkoxy, Cl~Cq-alkoxy-Cl-C~-alkyl or halo-Cl-C4-alkyl, or phenyl, substituted by Rl, R2, R3, R4 and ~5, in a suitable solvent, which can be the orthoester itself, or C) reacting a compound of general formula IV

H
N
~ 8J~ ~ IIV) Ar-N--I N NH2 ; ~ iD which Ar has the meaning given abov~ and R6 has the meaning given under B), with an ortho 2ster of general formula VII
~R8~C(ORg)~ (VII~
in which R8 and Rg have tbs mea~ings given under B), in a suitable solve~t, which can be the orthoester itself, to give a compound of formula : VITI

~: 25 5~4~

A r - N--51J~ N //l / 9 I V 1 1 1 6 R~

which i~ reacted with an isocyanate or isothiocyanate of formula V

R7-~CX (v) in which R7 and X ha~e the meanings given above in a suitable solvent, optionally in the presence of an acid acceptor and/or catalyst, or D~ reaceing a compound of general formula I~

~R7 N
Al - IN--S)~ N ~\ N ~\R8 ( IX) : R 0 in which:Ar, R7, R8 and X have the meanings given above~and R12 i~ hydrogen or a single equivalent of a metal, ~ith a compound o~ general : ~ formula X

R -~al (~
: 9 ~ - g _ ~3~5~

or of general ~ormula ~I
Rg-CO-Hal (XI) in.which Rg has the meani~g s~iven above, except hydrogen and Hal is cblorine or bromine, or .-of general for~ula XII
~9-C~-O-COR9 (XII) in which Rg has the meaning given above, in a suitable solvent, or E) reacting a compound of general formula XIII

~ ~R7 N N N
Ar-~SJ\N//~N~ R8 tXIII) H O

~: in which Ar, R7, R8 and ~ have the meaninys :~ given above, with a compound of general formula . XIV
M-Y (XIV) in which M is a single equivalent o~ a metal, and Y is Aydrogen, hydroxy, lower alkyl, lower alkoxy or an amino group, in a suitable solven~.
The particular reac~ion variants are preferably -~ 25 carried out in the presence of a diluent. For ~his purpose 3L3~S~

there are used solvents which are iner~ to the reactants.
Examples of such solvents or diluents are water~
aliphatic, alicyclic and aroma~i~ hydrocarbons, that can optionally be chlorina~ed, such as for example hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride and trichloroethane, ethers, such as for example diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones such as for example acetone, methyl ethyl ketone, methyl isopropy}
ke~one and methyl isobutyl ketone, nitriles, such as for example acetonitrile and propionitrile, alcohols, such as for example methanol, ethanol, isopropanol, butanol and ethylene glycol~ esters, such as for example e~hyl acetate ana amyl acetate, amides, such as for example dimethylformamide and dimethylacetamide, sulphones and sulphoxides, such as for example dimethyl sulphoxide and and sulpholane, and bases, such as for example pyridine.
The reaction Is suitably carried out between room temperature and the boiling point of the particular reaction mixture. The reaction can be carried out under atmospheric pressure but if desired higher or lower pressures can be used~
Process variant A is preferably carried ou~ in chlorinated hydrocarbons, such as dlchloromethane or ~3~53L~L

dichloroethane, in the presence of a catalyst and and/or acid acceptor. Examples o~ these are tertiary amines such as for exa~ple triethylamine, diisopropylethylamine, N-methylmorpholine, 4-dimethylaminopyridlne and pyridine.
Pyridine can be used both as catalyst and as a solvent.
Process variants B and C are preferably~ca~ried out in diluents such as, aliphatic, alicyclic and aromatic hydrocarbons, that can optionally be chlorinated, such as for example hexane, cyclohexane, petroleum ether, l;groin, benzene, toluene, methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride and trichloroethane, ethers, such as for example diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ~ ketones such as for e~ample acetone, methyl ethyl ketone, ; 15 methyl isopropyl ketone and methy} isobutyl ketone, nitriles, such as for example acetonitrile and propionitrile, esters, such as for example ethyl aceta~e and amyl acetate, amides, such as for example dimethylformamide and dimethylacetamide, snlphones and sulphoxides, such as for example dimethyl sulphoxide and and sulpholane, and bases, such as for example pyridine, and optionally in the presence of a catalyst and andfor acid acceptor. ~xamples of these are tertiary amines such as for example triethylamine, diisopropylethylamine, N-methylmorpholine, 4-dimethylamino pyridine and pyridine.

~L3~

Process variant D is preferably carried out by reacting a compound of general formula IX in a suitable solvent with a compound of general formula X, XI or XII, fil~ering off the salts which as general rule are highly insoluble and recovering ~he desired compounds after evaporation of the solvent.
Process varian~ E is preferably carried out by reac~ing a compound of general formula XIII in a suitable solvent with a metal base, such as a metal hydroxide, metal hydride, metal alkyl or metal amide, and the salts which as a general rule are highly insoluble can be recoverd by filtration or by evaporation of the solvent.
The compounds of the invention prepared by these processes can be isolated from the reaction mixtures in conventional manner, for example by distillation of the solvent at normal or reduced pressure, by precipitation with water or by extractlon.
:A higher level of purity can be achieved as a rule by column chromatography as well as by fractional distillation or crystal1lsation.
Tbe compounds of ~he invention are, as a rule~
colorl:ess or odourless crystals that are slightly soluble in water and in aliphatic~hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane and highly soluble 25 ~ in halogenated hydrocarbons, such as chloroform, methylene .~ , ~L3~

chloride and carbon teCrachloride, aromatic hydrocarbons such as benzene, ~oluene and xylene, e~hers, such as diethyl ether, tetrahydrofuran and dioxane, nitriles, such as acetonitrile~ alcohols, ~uch as met.hanol and ethanol, amides, such as dimethylformamide, and sulphoxides, such as dimethyl sulphoxide.
The sulphonyl chlorides of general formula III are new and can be prepared as described in the literature or by known methods by reac~ing a 2-benzylthio-6,7-dihydro-tl,2.4]triazolo~1.5-a]~1,3,5]~riazin-7-one of general formula XV

~U\ ,R7 ~7-CII -sJl\N~\N ~ IXV) in which R7, R8 and X have the meanings given above, wi~h chlorine in water or d water/acetic acid mixture.
Z0 Amines of general formula II, isocyanates and isothiocyanates of general for~ula V and or~hoesters of general formula VII are in the main commercially available or can be prepared by known processes or as described in the literature.
1 25 The compounds of the invention influence plant growth ~3~

and can therefore be used as plant growth regulators and especially as herbicides. Surprisingly, the compounds of the invention show a wide activity against monoco~yledonous and dicotyledonous weeds with good selectivity in crops. ~hether the compounds of the inven~ion act as total or selective herbicides depends mainly on the rates of use but also on the species and ~he time of use.
The compounds can be used in seed treatments, and in pre or post emergent use.
The co~pounds of the invention can used for example against the following plant species:
Dicotyledonous weeds of the species Polygonum, Sinapis, Atriplex, Spergula, 5tellaria, ~alium, Viola, Cirsium, Amaranthus, Ipomoea, Xanthium, Abutilon, Chenopodium, Cassia, Convolvulus, Mentha, Veronica, ~atricaria, Solanum, Lamium, Thlapsi, Capsella, Datura, Galinsoga, Mercurialis, Rhaphanus, vicia, Portulaca, Physalis, Sida, Anoda, Euphorbia, Myosotis, Centaurea, Brassica, Chrysanthemum and Helianthus;
Monocotyledonous weeds of the species Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, ; Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis.
Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, .

~3~5~

Agrostis, Alopecurus, ~pera, Rottboellia, Triticum and Hordeum.
The compounds can be used in important agricultural crops, such as wheat, barley, rice and soya beans.
S The use of the compounds of the invention is no~
limited to the weeds and crops mentioned above but can also be applied in a similar way to other plan~s.
The compounds are also suitable for weed control in industrial and railway installations and also roads and verges, with or without vegetation, in forests, woodlands, berry fruit and hop installations.as well as plantations.
The rates of use can vary over a wide range. They depend generally on the nature of the desired effects. In general the rates of use lie between 0.01 and 5 kg of active ingredient per hectare and;preferably for example ; in weed control between 0.1 and 0.5 kg of active ingredient per hectare.
The compounds of the invention can be used either alone or in admixture with one another or with other active agents. Optionally, other plant-protective agents or pesticides can be added, depending on the purpose for : ~
the treatment. When it is desired to broaden the spec~rum o~ activity, other herbicldes can also be added.

Herbicidally active mixing partners suitable in this connection include for example, the active agents listed ~' in ~eed Abstracts, vol. 34, No.5 (19B6) under the heading "Lists of co~mon names and abbreviations employed for currently used herbicides and plan~ growth regulators in Weed Abstracts~.
An improvement in the intensity and speed of action can be obtained, for example, by addition of suitable adjuvants, such as organic solvents, wetting agents and oils. Such additives may allow a decrease in the dose.
Suitable mixture partners may include phospholipids, e.g. phosphatidylcholine, hydrated phosphatidylcholines phosphatidylethanolamine, N-acyl-phosphatidylethanol-amines, phosphatidylinositol, pbosphatidylserine, lysolecithin or phosphatidylglycerol.
The designated active ingredients or their mixtures can suitable be used, for example, as powders, dusts, granules, solutions, emulsions or suspensions, wi~h the addition of liquid and/or solid carriers and/or diluents ;~ and, optionally, binding, wetting, emulsifying and/or dispersing adjuvants.
Suitable liquid carriers are, for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dime~hyl sulphoxide, dimethylformamide and other mineral-oil ~ractions and plant oils.
Suitable solid carriers include mineral earths, e.g.

- 17 _ S~L~4 bentonite, silica gel, talcum, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flours.
As surface-active agents there can be used for example calcium lignosulphonate, polyoxyethylenealkylphenyl ether, naphthalenesulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulpha~es, as well as substi~uted benzenesulphonic acids and their salts.
The peecentage of the active ingredient(s) in the 0 various preparations caD vary within wide limits. For example, the compositions can contain about lO to 90 percent by weight active ingredients, and about 90 to 10 percen~ by weight liquid or solid carriers, as well as, optionally up to ZO percent by weight of surfactant.
; 15 The agents can be applied in customary fashion, for example with water as the carrier in spray mixture volumes of approximately lOO to 1,000 l/ha. The agents can be appliea using low-volume or ultra-low-volume techniques or in the form of so-called microgranules.
The preparation of these formulations can be carried out in known manner, for example by milling or mixing processes. Optionally, individual components can be mixed just before use for example by the so-called commonly used tank-mixing method.

~3~

Formulations can be prepared, for example, from the following ingredients.
A~ Wettable Powder 1) 25 percent by weight active ingredient 60 percent by weight kaolin ; 10 percent by weight silicic acid 5 percent by weight of a mixture of calcium lignosulphonate and the sodium salt of N-methyl-N-oleyltaurine 2) ~0 percent by weight active ingredient 25 percent by weight bentonite 25 percent by weight colloidal silicic acid 10 percent by weight of a mixture of calcium lignosulphonate and alkylphenyl polyglycol ether B) Paste 45 percent by weigh~ active ingredient S percent by weight sodium aluminium silicate 15 percent by weight cetyl polyglycol ether with 8 mol ~ of ethylene oxide :~ 2 percent by weight spindle oll 10 percent by weight polyethylene glycol 2~ percent by weight water ~s~

C) Emulsifiable Concentrate 25 percent by weight acti~e ingrediene lS percent by weight cyclohexanone 55 percent by weight xylene 5 percent by weight of a mixture of calcium dodecylbenzenesulphonate and nonylphenol-polyoxyethylene.
The following examples illustrate the preparation of compound according to the invention.
ExamPle 1 N-(2,6-DichloroPhenYl)-6,7-dihydro-N,5,6-trimethyl-7-oxo-~, rl,2,41~riazolo~1,5-al[1,3,51triazine-2-sulphonamide (Process B) 1.30 g (3.4 mmol) 5-Amino-N-(2,6-dichlorophenyl)-N-m~thyl-l-(~ethylcarbamoyl)-1,2,4-tria~ole-3-sulphonamidewa s stirred in 10 ml triethyl orthoacetate with 5 drops glacial acetic acid for 12 hours at 120C. The insoluble residue was filtered and the filtrate concen~ra~ed. The product was chromatographed on silic~ gel using a mixture of hexane and ethyl acetate.
Yield: 0.77 g = 56~ of ~heory M.p.: 286-2B8C.
ElementarY analysis Calc. (%): C 38.72 H 3.00 N Z0.84 S 7.95 Cl 17.58 25 ~ound (%): C 38.~4 H 3.10 N 20.79 S 8.01 Cl 17.59 ~3~ 4 PreParation of the startinq material for Example 1 a) 5-Amino-N-(2,6-dichloroPhenYl)-N-n!e~hyl-l-(N-methyl-carbamoY12-1,2,4-triazole-3-sulpho~amide 2.0 g t6.2 mmol) 5-A~ino-N-(2,6-dichlorophenyl)-N-methyl-1,2,4-triazole-3-sulphonamide was suspended in 30 ml tetrahydrofuran and treated with 0.5 ml ~8.5 mmol) methyl isocyanate and 0.9 ml (6.5 mmol) trie~hylamine. The mixture was stirred for 3 hours at room temperature and allowed to stand overnight. The solution was concentrated and the residue chromatographed on silica gel using a mixture of hexane and ethyl acetate.
Yield: 1.36 g = 58% of theory M.p.: 220-~22C.
Elementarv analYsis 15 Calc. (%): C 34.84 H 3.19 N ~2.16 S 8.46 Cl 18.70 Found (%): C 34.80 H 3.6~ N 21.99 S 8.13 Cl 18.33 b) 5-Amino-N-(2,~=~ichloro2~nyl~-N-methyl-1,2,4-triazole-3-sul~honamide 9.80 g (22.8 mmol) of the pyridine salt of l-acetyl-20 5-amino-N-(2,6-dichlorophenyl)-1,2,q-triazole-3-sulphonamide was dissol~ed in 300 ml dimethylformamide and 0.89 g (29.7 mmol) 80% sodium hydride added portionwise a~ room temperature. The mixture was stirred for a further 30 minutes and 1.7 ~1 (27.a mmol) methyl iodide added. The Z5 mixture was allowed to stand overnight and concentrated.

~3~?S~

The residue was taken up in ZN aqueous sodium hydroxide a~d made slightly acidic by addition of 3N hydrochloric acid. The crystals wsre separated, washed with water and ether and recrystallised from acetonitrile.
Yield: 3.~ g = 96~ of theory M.p.: 259-255C.
ElementarY analysis Calc. t%): C 33.55 H 2.82 N 21.74 S 9.95 Cl 22~01 Found (%): C 3q.80 H 3.10 N 21.63 S 10.08 Cl 22.18 10 ExamDle 2 N-(2,6-Dichloro~henYl)-6,7-dihYdro-5,6-dimethYl-7-oxo-~1,2,41triazolo~1,5-a1~1,3,51triazine-2-sulphonamide (2.1 by process variant C) 3.4 g (9.0 mmol) N-(2,6-Dichlorophenyl)-5-(1-etXoxy-ethylidenamino)-lH-1,2,4-triazole-3-sulphonamide was stirred in 70 ml tetrahydrofura~ with 0.66 ml (11.3 m~ol) methyl isocyanate and 1.3 ml ~9.3 mmol) ~rie~hylamine for 4 hours at room temperature. The crystals were separated, washed with tetrahydrofuran~water 4:1, tetrahydrofuran and Z0 ether and dried in vacuo.
Yield: 3.4 g = 97% of theory M.p.: 331-339C.
Elementary analYsis Calc. (%): C 37.03 H 2.59 N 21.59 S 8.24 Cl 18.22 Found (%): C 37.21 H 2.60 N 21.22 5 8.59 Cl 18.35 ~3~5~

(2.2 by process variant A) 0.8a g (5.4 mmol) 2,6-Dichloroaniline was dissolved in 11 ml pyridine and treated with 1.67 g (6.0 mmol~
6,7-dihydro--5,6-dimethyl-7-oxo-[1,2,4~triazolo[1,5-a]~1,3,5 triazine-2-sulphonyl chloride. The mixture was stirred for 11 hours at 50C and for 5 hours at 75OC. The pyridine was distilled and the residue chromatographed with hexane~ethyl acetate.
Yield: 0.23 g = 10% of theory 10 M.p.: 331-334C.
PreParation of the startinq material for Example Z.l a) N-(2,6-DichloroPhenYl)-5-(1-ethoxyethylidenamino)-lH-; 1,2,4-triazole-3-sulphonamide 6.16 g ~20.0 mmol) 5-amino-N-(2,6-dichlorophenyl)-15 lH-1,2,4-triazole-1-sulphonamide was heated in 50 ml acetonitrile with 4.2 ml (23.0 mmol) triethyl orthoace~ate a~d 3 drops glacial acetic acid for 5 hours under reflux.
The mixture was cooled and e~aporated to dryness. The residue was recrystallised from ethyl acetate.
Yield: 6.1 g = 80~ of theory M.p.: 22Z-224C.
Elem ntarY analYsis Calc. (%): C 38.10 H 3.46 N 18.52 S 8.48 Cl 18.75 Found (%): C 3~.09 H 3.63 N 1~.64 S 8.57 Cl 1~.89 ~,:
- 23 ~

~3~

In a similar manner to these processes ~he following compounds were prepared.

Name of Compound _ Physical_Constant : 5 N-(2,6-Dichlorophenyl)-5-(1-ethoxymethylenamino)- mp:181-183QC
lH-1,2,4-triazole-3-sulphonamide N-(2,6-Dichlorophenyl)-5-(1-ethoxypropylidenamino~- mp:Z12-216C
lH-1,2,4-triazole-3-sulphonamide N-(Z,6-Dichlorophenyl)-5-(1-ethoxybenzylidenamino)- mp:213-217C
lH-1,2,4-triazole-3-sulphonamide N-(2,6-Dichloro-3-methylphenyl)-5-(1-ethoxyethyl- mp:202-204C
idenamino)-lH-1,2,4-triazole-3-sulphonamide ~ 5-(1-Ethoxyethylidenamino)-N-(2-methyl-6-nitro- ~p:195-197C
: phenyl)-lH-1,2,4-triazole-3-sulphonamide ~-(2-Chloro-6-fluorophenyl~-5-(I-ethoxye~hyl- mp:21~-215C
idenamino~-lH-1,2,4-triazole-3-sulphonamide 5-(1-Ethoxyethylidenamino)-N-(2,b-difluorophenyl)- mp:l87-188C
lN-1,2,4-triazole-3-sulphonamide N-(2,6-Dibromophenyl)-5-(1-ethoxyethylidenamino)- mp:l84-187C
lH-l,Z,4-triazole-3-~ulphonamide 5-(1-Ethoxyethylide~amino)-N-(2-trifluoro- mp:l24-125C
~: phenyl~-lH-1,2,4-triazole-3-sulphonamide 5-(1-Ethoxyethylidenamino)-N-phenyl- mp:164-166C
lH-1,2,4-~riazole-3-~ulphonamide 3L3~

Name of Compound _PhYsical Constan~
N-(2-Chlorophenyl~-5-tl-ethoxyethylidenamino)- mp:l50-15~C
lH-1,2,4-triazole--3-sulphonamide 5-(1-Ethoxyethylidenamino)-N-(2-methoxy-mp:l39-140C
5 phenyl)-lH-1,2,4-triazole-3-sulphonamide -b) 5-Amino-N-(2,6-dichloroPhenyl)-1,2,9-triazole=
;~ 3-sulphonamide 53.6 g (0.12 mol) of the pyridine salt of l-acetyl-10 5-amino-N-12,6-dichlorophenyl)-1,2,q~triazole-3-sulphonamide was dissolved in 200 ml 2N aqueous sodium hydroxide and stirred at room temperature for 10 minutes. With ice cooling it was brought to pH 5 with 2N hydrochloric acid.
The crystals were separated, washed with a small amount of water and ether and dried in ~acuo.
Yield: 35.4 g _ 92% of theory ~ M.p.~ 265-267C.
: Elementary analysis Calc. (%): C 31.18 H ? . 29 N 22.73 S 10.41 Cl 23.01 20 Found (%): C 31.38 H 2.40 N 22.37 S 10.23 Cl 22.23 c) l-AcetYl-5-amino-N-(2~6-dlchloropheny~ 2~g-triazole 3-sulPhonamide 42.63 g (0.26 mol) 2,6-dichloroaniline in 350 ml pyridine was treated with 54 g (0.29 mol) of l-acetyl-25 5-amino-1,2.4-~riazoIe-3-sulphonyl chloride and stirred at : - 25 -~S~4 60C for 12 hours. After cooling, the crystals were separated, washed with a small amount of pyridine and e~her and dried in vacuo.
Yield: 53.6 g = 52% of theory 5 M.p.: 213-215C.
Elementarv analYsis Calc. (~): C ~1.96 H 3.~9 N 19.58 S 7.~7 Cl 16.52 Found ~ C 41.89 H 3.33 N 19.36 S 7.46 Cl 15.97 d) l-Acetyl-5-amino-1,2,~-triazole-3-sulphonyl chloride 42.63 g (0.26 mol) 1-Acetyl-5-amino-3-benzylthio-1,2,4-~riazole was suspended in 1 litre water~acetic acid (1:1 mixture). At -10C chlorine was introduced over 2 hours at a such a rate that that the inner temperature remained below 0C. The resulting crystals were separated, washed with a small amount o~ wa~er and pentane and dried.
Yield: 74.5 g = 73.5% o~ theory .p.: 166-168C.
e) l-Acetyl-5-amino-3-benzYlthio-l,?,~-triazole To 30 g (0.145 mol) 5-amino-3-benzylthio-lH-20 1,2,9-triazole and 25 ml triethylamine in 300 ml methylene chloride, 12.57 g (0.16 mol) acetyl chloride in 30 ml methylene chloride was added dropwise. It was then stirred at room temperature for 30 minutes, treated with 160 ml lN
caustic soda and ~he proauct extracted with methylene chloride. After drying i~ was recrys~allised from ethyl ~3~5~

acetate.

Yield: 33 g = 91% of theory M.p.: 146C.
ElementarY analYsis 5 Calc. (~): C 53.20 H 4.87 N 22.55 S 12.91 Found (%): C 53.51 H 5.36 N 22.81 S lZ.81 f) l-~mino-3-benzYlthio-1,2,4-triazole 40.3~ g (0.35 mol) ~-Amino-5-mercapto-lH-1,2,s-triazole in 450 ml ethanol was treated with 13.9 g solid sdium hydroxide at room temperature. At room temperature, 44.30 g (0.35 mol) benzyl chloride chloride was added dropwise and the solution stirred overnight. The sal~ was filtered off, ethanol distilled and the residue recrystallised from ethyl acetate and dried.
15 Yield: 64.97 g = 90% of theory M.p.: 104C.
Elementary analysis Calc. (%~: C 52.~0 H 4.88 N 27.16 S 15.54 Found (%): C 52.10 H 4.84 N 27.48 S 15.11 PreParation of the startin~ material for ExamPle 2.2 a) 6J7-Dihydro-5,6-diMe hYl-7-oxo-tl~z~ltriazolo~l~5-a ; tl,3-51triazine-2-sulPhonyl chloride 3.00 (10.04 mmol) 2-benzylthio-6,7-dihydro-5,6-dimethyl-tl,Z,4]triaæolo[1,5-a~-tl,3,51triazin-7-one was suspended in 50 ml wa~e~/acetic acid (1:1 mixture). ~t - 27 _ ~3~4~

- 2~ -5 to 10C, chlorine was introduced over 45 minutes and the stirred for one hour, The resulting crystals were separated, washed with a small amount of water and ether and dried at 50C in vacuo.
Yield: 2.22 g = 80.7% of theory M.p.: 206-207C.
Elementary ana ly5 i S
Calc. (~): C 27.33 H 2.29 N 26.56 S 12.16 Cl 13.45 Found (%): C 27.51 ~1 2.69 N 26.33 S lZ.13 Cl 13.30 b) 2-BenzYlthio-6,7-dihYdro-5,6-dimethY~ 2~4ltria ~1,5-al-[1,3,51triazin-7-one ! 8.50 g (30.8 mmol) 3-Benzyltbio-5-(1-ethoxyethyliden-amino)-lH-1,2,4]triazole was dissolved in 250 ml tetrahydrofuran and treated with 3.73 g ~36.9 mmol) methyl isocyanate and 3.73 g (36.9 mmol) triethylamine. It was stirred for 5 hours at 70C, the solvent distilled and ; the residue treated with ether. The crystals were separated and recrys~allised from toluene.
Yield: 4.40 g = 49.8% of theory M.p.: 127-128~C.
Elementary analysis Calc. (%): C 5~.34 H g.56 N 2g.27 S 11.16 Found (g): C 5g.30 H g.79 N 24.33 S 10.96 ' .

c) 3-Benzylthio-5-(1-ethoxyethylidenamino)-lH-1,2,4]triazole 10.00 q (48.5 mmol) 5-amino-3-benzylthio-lH-1,2,4]triazole was suspended in 120 ml acetonitrile and reacted with 8 .38 g t53.3 mmol) triethyl orthoacetate and ~ drops glacial acetic acid. The mixture was heated for 6.5 hours under reflux, evaporated to dryness, taken up in hexane, with heating, filtered and again evaporated to dryness.
10 Yield: 10.89 g = 81.3% of theory M.p.: 89-90C.
ElementarY ana 1YS S
Calc. (%): C 56.50 H 5.8~ N 20.27 S 11.60 Found (~): C 56.59 H 5.37 N 20.58 S 11.92 15 Example 3 TriethYlammonium salt of N-t2,6-dichloroPhenYl~-~,7-dihYdro~ ~6-dimethyl-7-thioxo-~l~2~4ltriazolo[l~5-a [1~3~51triazine-2-sulPhonamide (By process variant C) 7.56 g (0.02 mol3 of (2,6-Dichlorophenyl~-5-(1-ethoxy-ethylidenamino)-N-lH-1,2,4-triaæole-3-sulphonamide was ~reated in 70 ml tetrahydrofuran with 1.7 ml ~0.025 mol) methyl isothiocyanate and 3.5 ml t0.025 mol) triethylamine and heated at 50C for 8 hours, The crystals were separated, washed ~ith te~rahydrofuran and e~her and dried ~3~

in vacuo.

Yield: 5.9 g = 53% of theo~y M.p.: 217-218C.

Elementar~ analYsis 5 Calc. ~%): C ~2.68 H ~.97 N 19036 S lZ.66 Cl 1~.00 Found (%): C ~2.83 H 4.82 N 19.3q S 12.69 Cl 14.13 ExamPle 4 (2,6-DichloroPhenyl)-6~?-dihydro-5~6-dimethyl-7-thi [1,2,41triazolo[1,5-al[1,3,5]triazine-2-sulphonamide 10 1.7 g (3.4 mol) of the triethylammonium salt of N-(2,6-dichlorophenyl)-6,7-dihydro-5,6-dimethyl-7-thioxo-~1,2,4]triaæolo~1,5-a][1,3,5]triaæine-2-sulphonamide was suspended in 100 ml water and acidified with lN
hydrochloric acid. The crystals were separated, was~ed ;~ 15 with water and ether and dried in vacuo.
Yleld: 1.3 g = 94% of theory M.p.: 301-302C.
ElementarY analYsis Calc. t~): C 35.56 H 2.99 N 20.74 S 15.82 Cl 17.50 20 Found t%): C 35.18 H 2.70 N 20.28 S 16.19 Cl 17.7g ~, .

~3~)S~

In a similar Manner to the Examples 1 to 4 the ~ollowing compounds of the invention were prepared.
Physical ExamPle _ _Name of Co~pound ConstantS N-(2,6-Dichloro-3-methylphenyl)-6,7-dihydro- mp:291-2q2C
5,6-dimethyl-7-thioxo-[1,2,9~triazolotl,5-a]-tl,3,5~triazine-2-sulphonamide 6 6,7-Dihydro-5,6-dime~hyl-N-(2-methyl- mp:242-244C
~-nitrophenyl)-7-thioxo-tl,2,~]triazolo-[1,5-a][1,3,53triazine-2-sulphonamide 7 N-(2-Chloro-6-fluorophenyl)-6,7-dihydro- mp:274-275C
5,6-dimethyl-7-thioxo-~1,2,41triazolo[1,5-a~-[1,3,5]triazine-2-sulphonamide 8 N-~2,6-Difluorophenyl)-6,7-dihydro- mp:Z84-2~5C
5,6-dimethyl-7-thioxo-[1,2,4~triazolotl,5-a]-tl,3,5]triazine-2-sulphonamide 9 N-~2,~-Dibromophenyl)-6,7-dihydro- mp:312-31~C
5,6-dimethyl-7-thioxo-[1,2,4]triazolotl,5-a~-- [1,3,5~triazine-Z-sulphonamide ;~ 20 10 6,7-Dihydro-5,6-dime~hyl-7-thioxo- mp:233-235C
N-(2-trifluoromethylphenyl)-~1,2,4~triazolo-~1,5-a] E 1,3,5]triazine-2-sulphonamide 11 6,7-Dihydro-5,6-dimethyl-N-phenyl- mp:Z31-233C
7-thioxo-[1,2,4]triazolotl,5-a]-~5 tl,3,5]triazine-2-sulphonamide ~L3~ 4 Physical Example Name of Compound Constant ~2 N-(2-Chlorophenyl~-6,7-dihydro-5"6-dimethyl- mp:200-206C
7-thioxo-C1,2,4]triazolo~1,5-a]-~1,3,5]triazine-2-sulphonamide 13 6,7-Dihydro-N-~2-methoxyphenyl)- mp:198-200C
5,6-dimethyl-7-thioxo-[1,2,~]triazolo-[1,5-a][1,3 J 5]triazine-2-sulphonamide ; lq N-(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-- mp:336-338C
5,6~dimethyl-7-oxo-~1,2,4]triazolo[1,5-a]-tl,3,5]triazine-2-sulphonamide 15 6,7-Dihydro-5,6-dimethyl-N-(?-methyl-6-nitrophenyl)-7-oxo-tl,2,4]triazolo-[1,5-a]~1,3,5]triazine-2-sulphonamide 16 N-(2-Chlo~o-6-fluorophenyl)-6,7-dihydro- mp:304-3060C
5,6-dime~hyl-7-oxo-~1,2,4]triazolotl,5-a]-[1,3,5]triazine-Z-sulphonamide 17 N-(2,6-Difluorophenyl)-6,7-dihydro- mp:29a-3oooc 5,6-dimethyl-7-oxo-[1,2,~]triazolQtl,5-a]-[1,3,5]triazine-Z-sulphonamide : 18 N-(2,6-Dibromophenyl)-6,7-dihydro- mp:327-3320C
~: 5,6-dimethyl-7-oxo-[1,2,;~]trlazolo-~ [1,5-a][1,3,53triazine-2-sulphonamide ::

:::
- ~2 -~3~:t5~

Physical Example Name of Compound Constant _ 19 6,7-Dihydro-5,6-di~ethyl-7-oxo- mp:268-270C
N-(2-~riPluoromethylphenyl)-tl,2,g]triazolo-t 1, 5-a ] L 1, 3~5]triazine-2-sulphona~mide 20 6,7-Dihydro-5,6-dimethyl-N-phenyl-7-oxo-[1,2,4~-triazolo[l r 5--a]-t 1, 3~s]triazine-2-sulphonamide ; 21 N-(2-Chlorophenyl)-6,7-dihydro- mp:20z-2060c ; 10 5,6-dimethyl-7-oxo-[1,2,4]triaæolo-~1,5-a][1,3,5]triazine-2-sulphonamide 22 6,7-Dihydro-N-(2-methoxyphenyl)- mp:358-359C
5,6-dimethyl-7-oxo-tl,2,4]triazolotl,5-a]-~1,3,5]triazine-2-sulphonamide 23 N-(2,6-Dichlorophenyl)-~-ethyl- mp:l79-180C
6,7-dihydro-5-methyl-7~thioxo-[1,2,4~-tria2010 ~ 1, 5-a ] t 1, 3,5]triazine-Z-~ulphonamide, triethylammonium salt 24 N-(2,6-Dichlorophenyl)-6-ethyl- mp:l85-186C
5,7-dihydro-5-methyl-7-oxo-tl,2,4]-trlazolo[l,5-a]~1,3,:5]triazine-2-su1phonamide, : triethylammonium salt ~5~

Physical xamPle _ Name of Compound Constant 25 N-(2,6~Dichlorophenyl)-6,7-dihydro- mp:233-Z35C
S-methyl-6-phenyl-7-thioxo-~1,2,~]-triazolo~l,5-a][1,3,S]triazine-2-sulphona~ide, trie~hylammonium salt 26 N-(2,6-Dichlorophenyl)-6,7-dihydro- mp:298-300C
5-methyl-6-phenyl-7-oxo-~1,2,~]-triazolo[l,5-a]~1,3,5]triazine-Z-sulphonamide 27 N-(Z,6-Dichlorophenyl)-6,7-dihydro-6-methyl-7-thioxo-~1,2,9]triazolo-L 1,5-a][1,3,5]trlazine-2-sulphonamide 28 N-(2,6-Dichlorophenyl)-6,7-dihydro- mp:296-300GC
6-methyl-7-oxo-[1,2,9]triazolo-:; 15 [1,5-a]~1,3,5]triazine-2-sulphonamide ~ ~ 29 N-~2,6-Dichlorophenyl)-6-ethyl-: 6,7-dihydro-7-thloxo-~1,2,~triazolo-~1,5-a]~1,3,5]triazine-2-sulphona~ide 30 N-(2,6-Dichlorophenyl)-6-ethyl- mp:285-287C
Z0 6,7-dihydro-:7-oxo-~1,2,4]triazolo-tl~5-a]~1~3~5~triazine-2-sulphonamide ; :~ 31 N-~2,6-Dichlorophenyl)-6,7-dihydro-:::
6-phenyl-7-thioxo-t~1,2,g]triazolo-: ~1,5-a]tl,3,5]triazine-2-sulphonamide ~: :

~3~

Physical Example Name oP ComPound Constant 32 N-(2,6-Dichlorophenyl)-6,7-dihydro- mp:262-265C
6-phenyl-7-oxo-[1,2,4]triazolo-[1,5-a][1,3,5]triazine-2-sulphonamide 33 N-t2,6-Dichlorophenyl)-5-ethyl-6,7--dihydro- mp:260-2620C
6-methyl-7-thioxo-[l,Z,4]triazolo-[1,5-a][1,3,5~triazîne-2-sulphonamide, triethylammonium salt 34 N-(2,6-Dichlorophenyl)-5-ethyl-6,7-dihydro- mp:288-291C
6-methyl-7-oxo-[1,2,4]triazolo-[l,S-a][1,3,5]triazine-2-sulphonamide, triethylammonium salt 35 N-(2,6-Dichlorophenyl)-5,~-diethyl- mp:185-187C
6,7-dihydro-7-thioxo-~l,Z,4]triazolo-~1,5-a][1,3,5]triazine-2-sulphonamide, triethy}ammonium salt 36 N-(2,6-Dichlorophenyl)-5,6-diethyl- mp:277-2~0C
6,7-dihydro-7-oxo-tl,~ triazolo-[1,5-a][1,3,5]triazine-2-sulphonamide, ~ triethylammonium salt : 37 N-(2,6-Dichlorophenyl~-5-ethyl-6,7-dihydro- mp:219-221C
6-phenyl-7-thioxo-[1,2,4~triazolo-[1,5-a]rl,3,5]triazine-2-sulphonamide, triethylammonium salt ~3~ 1L4~

Physical Example Name of Compound . Constant 38 N-~2,6-Dichlorophenyl)-S-ethyl-6,7-dihydro- mp:291-293C
6-phenyl-7-oxo-tl,2,4]triazolo-tl,5-a][1,3,5]triazine-2-sulphonamide, ~rie~hylammonium salt 39 N-(2,6-Dichlorophenyl~-6,7-dihydro-6-methyl- mp:270-272C
5-phenyl-7-thioxo-tl,2,4]triazolo-~1,5-a]tl,3,5]triazine-Z-sulphonamide, hydrate 40 N-~2,6-Dichlorophenyl)-6,7-dihydro-6-methyl- mp:201-203C
S-phenyl-7-oxo-~1,2,4]triazolo-[1,5-a]~1,3,5]triazine-2-sulphonamide, triethylammonium salt 41 N-~2,6-Dichlorophenyl)-6-e~hyl-6,7-dihydro-lS 5-Phenyl-7-thioxo-tl~2~4]tria2olo-[1,5-a3[1,3,5]triazine-2-sulphonamide 42 N-~2,6-Dichlorophenyl)-6-ethyl-6,7-dihydro- mp:209-212C
5-phenyl-7-oxo-[1,2,4]tria2010-[1,5-a]tl,3~5]triazine-2-sulphonamide, triethylammonium salt 43 N-(2,6-Dichlorophenyl)-6,7-dihydro-5,6-diphenyl-7-thioxo-tl,2,~]triazolo-tl,5-a]~1,3,5]triazine-2-sulphonamide .

~3~S~
_ ~7 _ Physical Example Name of Compound Constant ~4 N-(2,6-Dichlorophenyl)-6,7-dihydro- mp:225-227C
5,6-diphenyl-7-oxo-[1,2,4]triazolo-tl,5-a]tl,3,5]triazine-2-sulphonamide, triethylammonium salt 45 N-~2,6-Dichlorophenyl~-N-e~hyl-6,7-dihydro- mp:2~6-288C
5,6-dimethyl-7-oxo-tl,2,4]triazolo-l,5-a][1,3,5]tria~ine-2-sulphonamide 96 N-(2,6-Dichlorophenyl~-6,7-dihydro- mp:2g6-298C
; N,5,6-trimethyl-7-thioxo-[1,2,4]triazolo-[1~5-altl,3,5]triazine-2-sulphonamide 7 N-(2,6-Dichlorophenyl)-6,7-dihydro- mp:298-300C
:~ 5,6-dimethyl-7-oxo-tl,Z,4]triazolo-: ~ 15 tl,5-a]rl,3,5]triazine-2-sulphonamide, triethylammonium salt ~ ~
48 N-~2,6-Dichlorophenyl)-6,7-dihydro-:~
5,6-dimethyl-7-thioxo-[1,2,4]triazolo-tl,S-a]tl, 3J 5]triazine-2-sulphonamide, sodium salt 49 N-(2,6-Dichloro-3-me~hylphenyl)-6,7-dihydro- mp:20B-210C
::
5,6-dimethyl-7-thioxo-tl,2,4]triazolo-~l,S-a][1,3,5]triazine-2-sulphonamide, triethylammonium salt - 37 _ ~3~S~

Physical Example _ _ Name of Compound Constant 50 N-~2-Chloro-6-fluorophenyl)-6,7-dihydro- mp:l73-175C
5,6-dimethyl-7-thioxo-[1,2,~triazolo-[1,5-a][1,3,5]triazine-2-sulphonamide, triethylammonium salt 51 N-(2,6-Difluorophenyl)-6,7-dihydro- mp:l88-190C
5,6-dimethyl-7-thioxo-[1,2,9]triazolo-tl.5-a][1,3.53triazine-2-sulphonamide, ;10 triethylammonium salt 52 N-(2,6-Dibromophenyl)-6,7-dihydro- mp:301-305C
5,6-dime-thyl-7-thioxo-[1,2,4]triazolo-[1,5-a][1,3,5]triazine-2-sulphonamide, triethylammonium salt 53 6,7-Dihydro-5,6-dimethrl-N-(2-methyl- mp:l93-195C
6-nitrophenyl)-7-thloxo-Çl,2,4]triazolo-1,5-a][1,3,5~triazine-2-sulphonamide, triethylammonium salt 5q 6,7-Dihydro-5,6-dimethyl-7-~hioxo- mp:Z09-211C
N-(2-trifluoromethylphenyl)-tl,2,~]triazolo-[1,5-a][1,3,5~trlazine-2-sulphonamide, triethylammonium salt ' ~

:

- 3~3~

Physical Example _ Name of ComPound _ _ Constant 55 N-(2,6-Dichloro-3-methylphenyl)-6,7-dihydro- mp:306-309C
5,6-dimethyl-7-oxo-[1,2,4~triazolo-~1,5-a][1,3,5]triazine-2-sulphonamide, triethylammonium salt 56 N-~2-Chloro-6-fluorophenyl)-6,7-dihydro- mp:301-303C
5,6-dimethyl-7-oxo-[1,2,9]triazolo-tl,5-a]~1,3,5]triazine--2-sulphonamide, triethylammonium salt ; 57 N-(2,6-Di~luorophenyl)-6,7-dihydro- mp:300-302C
5,6-dime~hyl-7-oxo-[1,2,9]triazolo-~ [1,5-a][1,3,5]triazine-2-sulphonamide, : triethylammonium salt 58 6,7-Dihydro-N-(2-iodophenyl)- mp:213-218C
5,6-dimethyl-7-oxo-[1,2,4]triazolo-~ 1,5-a][1,3,5]triazine-2-sulphonamide ; 59 N-(2-Chloro--6-methylphenyl)-6,7-dihydro- mp:250-252C
5,6-dimethyl-7-oxo-rl,2,9~triazolo-tl;,5-a~[1,3,5]triazine-2-sulphonamid~e, triethylammoni:um salt ; 60 N-(2-Bromophenyl)-6,7-dihydro mp:l88-190C
~` 5,6-dimethyl-7-thioxo-~1,2,4}triazolo-~1,5-a]~1,3,5~triazine-2-sulphonamide : - 39 -~3~i~4 Physical Example Name of Compound Const~nt 61 N-(Z-Chloro-6-methylphenyl~-6,7-dlihydro- mp:266-267C
5,6-dimethyl-7-thioxo-~1,2,~]triazolo-[1,5-a][1,3,5]triazine-2-sulphonamide 62 N-~2-Chloro-6-meehylphenyl~-6,7-dihydro- mp:Z40-2420C
5,6-dimethyl-7-thioxo-~1,2,4]triazolo-tl,5-a][1,3,5]triazine-2-sulphonamide, triethylammonium salt 63 N-(2-Chloro-6-ethylphenyl)-6,7-dihydro- mp:246-248OC
5,6-dimethyl-7-thioxo-[1,2,4]triazolo-[1,5-a]~1,3,5]triazine-2-sulphonamide 6~ N-(2-Ethoxycarbonylphenyl~-6,7-dihydro- mp:l63-165C
5,6-dimethyl-7-thioxo-tl,2,4]triazolo-[1,5-a]~1,3,5]tria2ine-2-sulphonamide 65 6,7-Dihydro-5,6-dimethyl-N-(2-methylthio- mp:1~0-141C
phenyl)-7-thioxo-tl,2,9]triazolotl,5-a]-[1,3,5]triazine-2- ulphonamide, hydrate 66 N-(2-Ethoxycarbonyl-6-me~hylphenyl)- mp:168-170C
6,7-dihydro-5,6-dimethyl-7-thioxo-tl,Z~]triazolotl~5-a][l~3~5]triazine 2-sulphonamide 67 6,7-Dihydro-5,6-dimethyl-N-(2,3-dimethyl- mp:281-283C
6-nitrophenyl)-7-thioxo-~1,2,4]-tria~olo-E 1, 5-a]~1,3,5]triazine-2-sulphonamide, hydrate - so -~L3~51~

Physical Example _ _ Name of 50~pound c~n~n~
68 6,7-Dihydro-N-(2-methoxycarbonyl-6-methyl- mp:212-213C
phenyl)-5,6-dimethyl-7-thioxo-tl,2,~]triazolo-r 1,5-a][1,3,5]triazine-2-su}phonamide 69 N-(2-Bromophenyl)-6,7-dihydro- mp:l83-187C
5,6-dimethyl-7-thioxo-~1,2,9]triazolo-~1,5-a][1,3,5]triaæine-2-sulphonamide 70 6,7-Dihydro-N-(2-methoxycarbonylphenyl)- mp:2~4-2~6C
5,6-dimethyl-7-oxo [1,2,~]triazolo]-[1,5-a][1,3,5]triazine-2-sulphonamide 71 N-t2-Ethoxycarbonylphenyl)-6,7-dihydro- mp:233-236C
5,6-dimethyl-7-oxo-11,2,4]triazolo-[1,5-a]tl,3,5]triazine-2-sulph~onamide 72 6,7-Dihydro-N-(2-isopropoxycarbonylphenyl)- mp:Z44-246C
: 5,6-dimethyl-7-oxo-~I,2,4]tria2010]-[1,5-a]tl,3,5]~riazine-2-sulphonamide 73 N-(2-Chloro-6-ethylphenyl~-6,7-dihydro- mp:275-2770C
5,6-dimethyl-7-oxo-[1,2,4ltriazolo-~ 20 tlj5-a][1,3,5]triazine-2-sulphonamide : 79 N-(2-Acetylphenyl)-6,7-dihydro- mp:2Z5-227c 5,6-dimethyl-7-oxo-tl,2,~]tria olo-[1,5-a]~1,3,5]triazine-2-sulphonamide :, .

-- ql --~3~

Physical Example Name o Compound Con~tant 75 6,7-Dihydro-N-(2-isopropyl-6-m~thylphenyl)- mp:28g-285C
5,6-dimethyl-7-oxo-[1,2,4]~riazolo]-[1,5-a][1,3,5]triazine-2-sulphonamide 76 6,7-Dihydro-N-(2-methoxycarbonyl-6-methyl- mp:Z57-258C
phenyl)5,6-dimethyl-7-oxo-[1,2,g]triazolo]-; [1,5-a][1,3,5]triazine-2-sulphonamide 77 6,7-Dihydro-N-(2-isopropyl-6-methylphenyl)- mp:253-254C
5,6-dimethyl-N-(methylcarbamoyl)-7-oxo-~1,5-a~1,2,g]triazolo]tl,3,5]triazine-2-sulphonamide 78 N-t2-Fluorophenyl)-6,7-dihydro- mp:22~-231C
5,6-dimethyl-7 oxo-~1,2,~]triazolo-~1,5-a~tl,3,5]triazine-2-sulphonamide 79 N-(~-Bromo-4-fluorophenyl)-6,7-dihydro- mp:234-2350C
5,6-dimethyl-7-oxo-[1,2,4]triazolo[1,5-a~-~1,3,5]triazine-2-sulphonamide, hydrate 80 N-(2,6-Dichlorophenyl)-6,7-dihydro- mp:298-300C
5-methyl-7-oxo-tl,2,4]triazolo-tl~5-a][l~3~5]tria2ine-7-sulphonamide 81 6,7-DihydrG-N-(2-iodophenyl)- mp:l92-lssC
5,6-dimethyl-7-thioxo-[1,2,4]~riazolo3-tl,5-a3[1,3,53triazine-2-sulphonamide ~s~
- ~3 -Physical Example _ Name o~ Compound _ _ Constant _ 82 6,7-Dihydro-N-(2-isopropyl-6-methylphenyl~- mp:269-Z71C
5,~-dimethyl-7-thioxo-~1,2,4]triazolo]-tl,5-a]tl.3,5]triazine-2-sulphonamids 83 ~-(Z-Bromo-6-chloro-4-fluorophenyl)- mp:Z71-Z73C
6,7-dihydro-5,6-dimethyl-7-thioxo-[l,Z,43-tria2010~1,5-a~tl,3,5]triazine-2-sulphonamide 84 N-(2-Bromo-6-methoxy)-6,7-dihydro- mp:Z29-231C
5,6-dimethyl-7-thioxo-[1,2,4]triazolo-tl,5-a]tl,3,5]triazine-2-sulphonamide 85 6,7-Dihydro-N-(2,6-dimethylphenyl)- mp:263-2650C
; 5,6-dimethyl-7-thioxo-[1,2,4]triazolo~-~1,5-a]tl,3,5}triazine-2-sulphonamide, hydrate 86 6,7-Dihydro-5~6-dimethyl-7-oxo- mp 240-242C
N-qu~inolin-8-yl-tl,2,4~triazolo]-` C1,5-a]tl,3,5]triazine-z-sulphonamide 87 N-(4-Bromo-2,6-dichlorophenyl)-6,7-dihydro- mp 283-285C
,. 5,6-dimethyl-7-thioxo-tl,2,4]-triazolo--[1,5-a][1,3,5]triazine-2-sulphonamide, hydrate 88 6,7-Dihydro-5,6-dimethyl-N-quinolin-8-yl- mp:l37-139C
: 7-thioxo-~1,2,4]triazolo~-~1,5-a}[1,3,5}triazine-2-sulphonamide ~ :
:: :
~ - 43 -,~

~30S~

- g4 -Physical Example Name of Compound Constant 8g ~,7-Dihydro-N-(2-methoxycarbonyl- mp:222-224C
3,6-dimethylphenyl~-5,6-dimethyl-7-thioxo-[1,2,4]triazolo]-tl,5-a]~l,3,5]triazine-2-sulphonamide 90 6,7-Dihydro-N-(2-methoxycarbonyl- mp:194-195C
5,6-dimethylphenyl)-5,~--dimethyl-7-thioxo-~1,2,4]triazolo]-[1,5-a][1,3,5]triazine-2-sulphonamide 91 N-(2-Bromo-6-chlorophenyl)-6,7-dihydro- mp:304-305C
5,6-dimethyl-7-thioxo-[1,2,4~-triazolo-~1,5-a][1,3,5]triazine-2-sulphonamide 92 6,7-Dihydro-N-(2-methoxycarbonyl-3,6-dimethyl- mp:225-227C
: 15 phenyl)-5,6-dime~hyl-7-oxo-[1,2,4]triazolo]-~1,5-a]~1,3,5~triazine-2-sulphonamide 93 6,7-Dihydro-N-(Z-methoxycarbonyl-5,6-dimethyl- mp:Z16-218~C
phenyl)-5,6-dimethyl-7-oxo-Ll,2,g3triazolo]-~1,5-a]l1,3,5]triazine-2-sulphonamide 9~ N-(2-Bromo-6-chlorophen~1)-6,7-dihydro- mp:321-322C
5,6-dimethyl-7-oxo-~1,2,4]-triazolo-El,5-a]~l,3,5~triazine-2-salphonamide 95 N-t2-Ethoxycarbonyl-6-methylphenyl)- mp:l95-197C
6,7-dihydro-5,6-dimethyl-7-oxo-~1,2,4~-triazolo~ -a~[1,3,5~triazine-2-sulphonamide 5~

The following examples illustra~e ~he posibilties ~or areas of use of the compound~ o~ the inve~tion.
EX~MPLE A
In a greenhouse, the compounds given below were applied at a rate of l.0 kg active ingredien~/ha., suspended in 500 litres water/ha, to t:he test plants of the species Helianthus and Chrysathemum in pre- and post-emergent uses.

; lO The damage to the weeds was assessed three weeXs after : treatment, on a score of 0 to 4, in which:

0 2 no activity l = medium growth chec~
:~ lS Z = heavy growth check :~ 3 = full growth check 4 = total destruction : It was shown that the ~ompounds of Examples l to 14, 16 to 19, Zl to 26, 28, 30, 32 to 40, g3, 44 to 47 and 49 to 95 caused 100% ~=4) destruction of the plants in this test both in pre- and post-emergent application to the test plants.

: 25 5 _ ~3~5~

EXAMPLE B
Seeds of mono- and dicotyledonous weeds as well as of the crops wheat (Triticum aestivum), barley (Hordeum distichum~ and rice (Oryza sativa) were plan~ed in pots with humus-containing sandy soil and covered with earth.
In a greenhouse, the compounds of the invention given below, were applied as a suspension in 500 litres of water/ha at a rate of 0.1 kg of active compound/ha, to the upper soil layer before emergence of the plants.
After treatement the test pots were placed in a greenhouse and the test plants grown under good growth conditions. Four weeks after the treatment plant damage was assessed. Untreated contols were used for comparison.
As the table clearly shows all ~he weeds were destroyed without damage to ~he crop plants.
In the following table:
0 = no activity 4 - total destructi~n oP the plant.
Tr = Triticum aestivum Ho = Hordeum distichum Or ~ ~yza sa~iva Se = Setaria sp.
He = Helianthus sp.
~; St = Stellaria sp.
Ab = Abutilon sp.

~ ` ~3~
- g7 -Vi = Viola sp.
Br = Brassica sp.
So = Solanum sp.
Ma = Matricaria sp.
Cy = CYperU~ sp.
Ec = Echinochloa sp.

Compounds of invention Tr Ho Or Se He St Ab Vi Br So Ma CY Ec Example 3 0 0 0 4 9 ~ 4 ~ 9 4 4 3 9 Example 4 0 0 0 4 4 4 4 4 4 4 4 3 q .

Control 0 0 0 0 0 0 0 0 0 o 0 0 EXAMPLE C
Seeds of mono- and dicotyledonous weeds as well as o~
the crops wheat (Triticum aestivum3, barley (Hordeum distichum) and rice (Oryza sativa) were planted in pots ~ith humus-containing sandy soil and couered with earth.
In a greenhouse, the compounds of ~he invention given below, were applied as a suspension in 500 litres of water/ha at a rate of 0.1 kg of active compound/ha, to the upper soil layer before emergence of the plants.
After treatement the test pots were placed in a ~ 7 -~3~t5~
- ~8 -greenhouse and the test plants grown under good growth conditions. Two weeks a~ter the treatment plant damage was assessed. Untreated contols were used for comparison.
AS the table clearly shows al} the weeds were destroyed without damage to the crop plants.
In the following ~able:
O = no activity 4 = total destruction of the plan~.
Tr = Triticum aestivum Ho = Hordeum distichum Or = OEyxa sativa Se = Setaria sp.
He = Helianthus sp.
St = Stellaria sp.
Ab = Abutilon sp.
Vi = Viola sp.
Br = Brassica sp.
So = Solanum sp.
Ma = Matricaria sp.
Cy = CYperus sp.
Ec = Echinochloa sp.

- q8 -5~4~
_ gg _ Compounds of invention Tr Ho Or Se He S~ Ab Vi Br So Ma Cy Ec Example 3 o O 0 4 4 4 4 9 4 4 4 3 4 Control o O O O O O o o o O O O o EXAMPLE D
In a greenhouse, the compounds of the invention shown in the table were applied at the rates given. For this the compounds were applied in vessels containing 1500 ml. As test plants there were used Echinochloa crus-galli, Fimbrystylis miliacea, Paspalum distichum and Cyperus difformis in the Z to S leaved stage.

In the table the scores have the following meanings:

:
: O = no activity 1 = slight damage : ZO 2 = intermediate damage 3 = heavy damage 4 = total destruction : ~ ' : - 49 -~3~

so Ec = Echinochloa crus-galli Fi - Fimbristylis miliacea Pa = Paspalum distichum Cy = Cyperus difformis Compound of Water application ~he invention ppm Ec Fi Pa Cy -E~ample 2 30 ~ 4 g 4 10 Example 3 30 9 g 4 4 :'~

~ - 50 _ ,:

Claims (5)

1. 6,7-Dihydro-[1,2,4]triazolo[1,5-a][1,3,5]triazine-

2-sulphonamides of general formula I

(I) in which Ar is a phenyl, naphthyl, pyridyl or thienyl group of general formula R1, R2, R3, R4 and R5 are the same or different and are hydrogen, a C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy, halo-C1-C4-alkyl, C1-C4-alkoxy, halo-C1-C4-alkoxy. C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl, halogen, C1-C4-alkoxy, a group R9-O-CO, a carbamoyl group , an amino group , cyano, nitro, a sulphur containing group R9-S(O)n-, an acyl group R9-CO, a group R9-O-CO-(CH2)n, or phenyl or phenoxy, both of which are optionally substituted by one or more of C1-C4-alkyl, halo or nitro, R6 is hydrogen, an acyl group R9-CO, a group R9-O-CO-, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, phenyl-C1-C4-alkyl, a carbamoyl group , an alkali metal atom, a single metal equivalent of an alkaline earth or other metals or ammonium group, optionally substituted by C1-C6-alkyl, R7 and R8 are the same or different and are hydrogen, a C1-C5-alkyl, C2-C6-alkenyl or C2-C6-alkynyl group, each of which is optionally substituted by halo and/or C1-C4-alkoxy, a phenyl-C1-C6-alkyl, phenyl-C2-C6-alkenyl or phenyl-C2-C6-alkynyl group, each of which is optionally substituted by halo, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl or halo-C1-C4-alkyl, phenyl, substituted by R1, R2, R3, R4 and R5, an acyl group R9-CO, a group R9-O-CO, a group R9-O-CO-(CH2)n, a carbamoyl group, or a sulphonyl group R9-SO2.
R9 is hydrogen, a C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or phenyl-C1-C4-alkyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy or C1-C4-alkoxy, or phenyl, optionally substituted by halo, nitro or C1-C4-alkyl, R10 and R11 are the same or different and are hydrogen, a C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl group, each of which is optionally substituted by one or more of the same or different halo, hydroxy or C1-C4-alkoxy, or R10 and R11 together with the adjacent nitrogen form a pyrrolidinyl, piperidino or morpholino ring, X is oxygen or sulphur, and n is 0, 1 or 2.
2. 6,7-Dihydro-[1,2,4]triazolo[1,5-a][1,3,5]triazine--2-sulphonamides according to claim 1, in which Ar is a phenyl group of general formula R1 and R5 are the same or different and are halogen, methyl, trifluoromethyl, nitro, methoxy or methoxycarbonyl, R2, R3 and R4 are the same or different and are hydrogen, halogen, trifluoromethyl or a C1-C4-alkyl group, R6 is hydrogen, a single equivalent of a metal or a C1-C4-acyl group, and R7 and R8 are the same or different and are hydrogen, C1-C4-acyl, C1-C6-alkyl, C2-C4-alkenyl or phenyl.

3. A herbicidal and plant-growth regulant composition which comprises a compound according to claim 1 or 2, in admixture with carriers and diluents.

4. A method of combating weeds which comprises applying to the weeds or their locus a compound according to claim 1 or 2.

5. A method of regulating the growth of plants which comprises applying to the plants or their locus a plant growth regulant amount of a compound according to claim 1 or 2.